铜催化的自由基不对称碳–硫和硫–氧交叉偶联反应研究

手性α-烷基硫化合物是有机合成和生化过程中不可或缺的合成砌块，也是构建生物大分子、药物和农药等重要的组成成分。因而，发展不对称催化方法来高效构建手性碳–硫键是现代合成化学和生物学的一个重要研究方向。在这方面，两电子离子型反应取得了长足的进展，但存在着底物范围窄和产物结构单一等不足。另外，由于金属–硫键异裂困难，过渡金属催化的反应机理多为硫亲核试剂对手性金属物种的球外进攻来构筑碳–硫键，限制了反应类型的拓展。因此，亟需发展新颖的催化体系来构建多种类型的手性α-烷基硫化合物。本文通过模拟天然酶催化自由基均裂取代的机制，利用一价铜/富电子阴离子手性配体催化体系实现了自由基立体汇聚式碳–硫交叉偶联反应，反应的底物适用性广，可以兼容不同类型的外消旋二级、三级卤代烷烃和易于转化的硫亲核试剂，并展现出良好的官能团耐受性。

该催化体系可以有效启动反应产生烷基自由基，同时提供良好的手性环境来调控反应的对映选择性，并且能够很好地抑制非手性背景反应以及自由基副反应。三种不同骨架的阴离子手性N,N,P(N)-配体可以分别实现苄溴/氯、炔丙基溴和三级α-氯代酰胺的自由基立体汇聚式碳–硫交叉偶联反应，成功合成了91个手性硫代磺酸酯和手性季碳硫酯化合物，产率最高达99%，ee值最高达97%。

该策略提供了一个灵活且实用的平台来制备不同类型的手性α-烷基硫化合物，产物经过简单的转化可以得到手性硫醇、硫醚、二硫醚、多氟硫烷、亚砜、砜、亚砜亚胺、磺酰胺和磺酰氟等。降低催化剂载量到2.5 mol%能够以较好的反应产率和ee值实现克级规模的放大反应，进一步证明了该方法学的合成实用性和潜在应用价值。

机理研究实验表明配体螯合的一价铜硫物种是引发反应，还原卤代烷烃为潜手性烷基自由基的关键中间体。自由基捕获实验和自由基钟实验支持了反应体系中有自由基活性中间体的产生。动力学时间淬灭实验认为反应是经过统一的立体汇聚式转化历程来制备手性产物。DFT理论计算结果支持了手性碳–硫的成键倾向于仿生自由基取代的反应机制。该催化体系为强配位杂原子亲核试剂参与的不对称碳–杂键构建反应提供了新策略。

通过自由基均裂取代的反应机制还实现了一价铜/阴离子手性磺酰胺N,N,N-配体催化的芳基磺酰氯和2-氨基-1,3-二醇的对映选择性硫–氧交叉偶联反应，避免了过渡金属催化杂–杂偶联反应中双电子还原消除困难的问题。成功合成了11个2-氨基手性磺酸酯类化合物，产物还可以通过简单的转化构建2-氨基手性硫醚、膦化合物以及非天然氨基酸，表明了该方法具有潜在的实用性。机理实验研究表明，芳基磺酰氯与配体螯合的一价铜催化剂发生单电子转移产生磺酰基自由基，并且磺酰基自由基参与了对映选择性硫–氧成键的过程。

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